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Isotopic Effects

At this point it can be clearly seen the dependence upon mass of the dipole moment derivative,since tex2html_wrap_inline479 is a normal coordinate. Recall that the normal coordinate is a orthogonalized mass-weighted Cartesian coordinate so different isotopomers will have different normal coordinates.

Pictorially, look at Figure 4. Here is a plot of dipole moment s for a system with only two normal coordinates, tex2html_wrap_inline481 and tex2html_wrap_inline483. For a given displacement of tex2html_wrap_inline481 and tex2html_wrap_inline483, the dipole moment was plotted. The components of the dipole moments along each coordinate has also been projected. The gradient of the dipole moment with respect to a normal coordinate will be greatest for a component that is perpendicular to the curves. Likewise, if the component should run long a curve, the gradient will be very small. As such, component tex2html_wrap_inline489 will have a more intense transition than component tex2html_wrap_inline491. Now, for an isotopically substituted system, represented by tex2html_wrap_inline493 and tex2html_wrap_inline495, the coordinate system has rotated with respect to the dipole and the new components are now much more similar in intensity since their gradients are almost identical.



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Tue Aug 12 10:50:18 EDT 1997